EP0266694A2 - Durch Amid modifizierte Epoxydharze - Google Patents

Durch Amid modifizierte Epoxydharze Download PDF

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Publication number
EP0266694A2
EP0266694A2 EP87115970A EP87115970A EP0266694A2 EP 0266694 A2 EP0266694 A2 EP 0266694A2 EP 87115970 A EP87115970 A EP 87115970A EP 87115970 A EP87115970 A EP 87115970A EP 0266694 A2 EP0266694 A2 EP 0266694A2
Authority
EP
European Patent Office
Prior art keywords
component
moles
epoxy resin
ratio
average
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP87115970A
Other languages
English (en)
French (fr)
Other versions
EP0266694A3 (de
Inventor
James L. Bertram
Willie L. Myles
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Publication of EP0266694A2 publication Critical patent/EP0266694A2/de
Publication of EP0266694A3 publication Critical patent/EP0266694A3/de
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/64—Amino alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4284—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with other curing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/56—Amines together with other curing agents
    • C08G59/58—Amines together with other curing agents with polycarboxylic acids or with anhydrides, halides, or low-molecular-weight esters thereof

Definitions

  • the present invention pertains to amide modified epoxy resins which are suitable in the preparation of coatings and the like.
  • the coatings industry is constantly seeking ways and means to eliminate or reduce the amount of organic solvents released into the atmosphere. Therefore, it is desirable to employ water dilutable resinous compositions in the preparation of such coatings.
  • the present invention provides a resin which when neutralized with a base becomes water soluble or water dispersible thereby resulting in stable solutions or dispersions.
  • One aspect of the present invention pertains to a curable amide modified epoxy resin prepared by reacting the reaction product of (A) the reaction product of (1) at least one epoxy resin having an average of more than one 1,2-epoxy groups per molecule and an average of from zero to 30 aliphatic hydroxyl groups per molecule and (2) (a) at least one dialkanolamine and (b) at least one monoalkanolamine wherein components (a) and (b) are added sequentially with component (a) being added first or components (a) and (b) are added as a mixture; with (B) at least one anhydride of a saturated or an ethylenically unsaturated dicarboxylic acid; and wherein the components are employed in quantities which provide (i) a ratio of moles of component (A-2-a) to epoxy equivalent contained in component (A-1) of from 0.55:1 to 0.95:1, preferably from 0.75:1 to 0.9:1; (ii) a ratio of moles of component (A-2-b) to epoxy equivalent
  • Another aspect of the present invention pertains to a curable amide modified epoxy resin prepared by polymerizing (I) the reaction product of (A) the reaction product of (1) an epoxy resin having an average of more than one 1,2-epoxy group per molecule and an average of from zero to 30 aliphatic hydroxyl groups per molecule and (2) (a) a dialkanolamine and (b) a monoalkalanolamine; wherein the components (a) and (b) are added as a mixture or sequentially with component (a) being added first; with (B) an anhydride of an unsaturated dicarboxylic acid; with (II) a polymerizable ethylenically unsaturated monomer or mixture of monomers; wherein (i) the ratio of moles of component (I-A-2-a) to epoxy equivalent contained in component (I-A-1) is from 0.5:1 to 0.95:1, preferably from 0.75:1 to 0.9:1; (ii) the ratio of combined moles of component (I-A-2-
  • Another aspect of the present invention pertains to a water soluble or water dispersible product resulting from neutralizing the aforementioned amide modified epoxy resins with a base.
  • Another aspect of the present invention pertains to coatings prepared from said amide modified epoxy resin and to coatings prepared from said neutralized amide modified epoxy resin.
  • the reaction between the epoxy resin and the mixture of primary and secondary amines can be conveniently conducted at a temperature of from 25°C to 200°C, preferably from 60°C to 150°C. If desired, the reaction can be conducted in the presence of a suitable reaction medium such as, for example, aliphatic or aromatic hydrocarbons, ketones, glycol ethers, alcohols, ethers, esters, and combinations thereof.
  • a suitable reaction medium such as, for example, aliphatic or aromatic hydrocarbons, ketones, glycol ethers, alcohols, ethers, esters, and combinations thereof.
  • Particularly suitable solvents which can be employed as a reaction medium include, for example, methanol, ethanol, isopropanol, butanol, cyclohexanol, 2-­ butoxyethanol, 2-methoxyethanol, 2-ethoxyethanol, 2-­methoxypropanol, 2-butoxypropanol, toluene, xylene, cumene, tetrahydrofuran, dioxane, acetone, methylethyl ketone, methylisobutyl ketone, cyclohexanone, and combinations thereof.
  • the polymerization of the ethylenically unsaturated monomers with the unsaturated dicarboxylic acid anhydride reaction product is conveniently conducted in the presence of a free radical catalyst such as organic peroxides, azo compounds, combinations thereof and the like.
  • catalysts include, for example benzoyl peroxide, t-butylper­benzoate, di-tert-butylperbenzoate, t-butylperoctoate, azobisisobutyronitrile t-butylazo-2-cyano-4-methyl pentane, t-butylazo-4-cyanovaleric acid, t-butylazo-2-­phenyl-4-methyl pentane, t-butylazo-2-phenyl propane, 1-cyano-1-(t-buty-lazo)-cyclohexane, 2-t-butylazo-1, 1-­diethoxycarbonyl-2,4- dimethyl pentane, and combinations thereof.
  • Suitable epoxy resins which can be employed herein include any epoxy resin having an average of more than one 1,2-epoxide group per molecule and an average of from zero to 30, preferably from 4 to 20 aliphatic hydroxyl groups per molecule.
  • the higher aliphatic hydroxyl-containing epoxy resins can be conveniently prepared by reacting a relatively low equivalent weight epoxy resin having an average of more than one 1,2-epoxy group per molecule with a material having an average of more than one hydroxyl group per molecule.
  • Particularly suitable epoxy resins include those prepared by reacting a diglycidyl ether of an aromatic dihydroxyl-containing compound with an aromatic dihydroxyl-containing compound.
  • aromatic dihydroxyl-containing compounds include those represented by the formulas wherein A is a divalent hydrocarbyl group having from 1 to 12, preferably from 1 to 6, carbon atoms, -O-, -S-, -S-S-, - -, each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to 10, preferably from 1 to 4, carbon atoms, or a halogen atom, preferably chlorine or bromine and n has a value of zero or 1.
  • dihydroxyl-containing compounds include, for example, bisphenol A, bisphenol F, resorcinol, catechol, hydroquinone, halogenated or alkyl or alkoxy substituted derivatives of such dihydroxyl-containing compounds, and combinations thereof. These dihydroxyl-containing compounds can be the same or different from those from which the epoxy resin was prepared.
  • Said epoxy resins can be prepared by dehydro-halogenating the reaction product of a dihydroxyl-containing compound with an epihalohydrin such as epichlorohydrin, epibromohydrin, epiiodohydrin as well as alkylated derivatives thereof such as, for example, methylepichlorohydrin, methylepibromohydrin, methylepiiodohydrin, and combinations thereof.
  • an epihalohydrin such as epichlorohydrin, epibromohydrin, epiiodohydrin as well as alkylated derivatives thereof such as, for example, methylepichlorohydrin, methylepibromohydrin, methylepiiodohydrin, and combinations thereof.
  • Suitable monoalkanoloamines which can be employed herein include, for example, those represented by the formula X ⁇ -R-NH2 (III) wherein R is a divalent hydrocarbyl or hydrocarbyloxy group having from 2 to 9 carbon atoms and X ⁇ is hydroxyl.
  • Particularly suitable primary amines which can be employed herein include, for example, ethylamine, propylamine, butylamine, aniline, benzylamine, ethanolamine, methoxyethylamine, methoxypropylamine, ethoxyethylamine, ethoxypropylamine, ethoxybutylamine, butoxyethylamine, butoxypropylamine, butoxybutylamine, nitrobenzylamine, and combinations thereof.
  • hydrocarbyl as employed herein means any aliphatic, cycloaliphatic, aromatic, aryl substituted aliphatic or aliphatic substituted aromatic groups.
  • Suitable dialkanolamines which can be employed herein include, for example, those represented by the formula X ⁇ -R-N- -R-X ⁇ (IV) wherein each X and R are independently as defined above.
  • Particularly suitable secondary amines which can be employed herein include, for example, diethylamine, dipropylamine, dibutylamine, diethanolamine, methylethanolamine, ethylethanolamine, bis(methoxyethyl)amine, bis(ethoxyethyl)amine, bis(methoxypropyl)amine, bis(butoxyethyl)amine, bis(butoxy-propyl)amine, bis(butoxybutyl)amine, and combinations thereof.
  • Suitable phenols include besides phenol, those substituted with hydrocarbyl groups having from 1 to 10 carbon atoms, halogen atoms, particularly chlorine or bromine, and the like.
  • Particularly suitable phenols include, for example, phenol, o-cresol, nonylphenol, chlorophenol, dichlorophenol, trichlorophenol, bromophenol, dibromophenol, tribromophenol, butylphenol, and combinations thereof.
  • Suitable ethylenically unsaturated dicarboxylic acid anhydrides which can be employed herein include, for example, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, citra­conic anhydride, itaconic anhydride, dodecenylsuccinic anhydride, maleic anhydride adducts of linoleic acid, cyclopentadiene or methylcyclopentadiene, combinations thereof and the like.
  • the carboxylic acid anhydride is added to the modified epoxy resin at a temperature of not greater than 100°C, preferably not greater than 75°C. At temperatures greater than 100°C, too much of the anhydride undesirably reacts with the aliphatic hydroxyl groups instead of the secondary amine groups resulting from the reaction between the epoxy resin and the primary amine compounds.
  • Suitable polymerizable ethylenically unsaturated compounds which can be employed herein include, for example, styrene, alpha-methylstyrene, halogenated styrene, butadiene, alkyl or hydroxyalkyl acrylates, alkyl or hydroxyalkyl methacrylates, acrylic acid, methacrylic acid, acrylonitrile, methacryilonitrile, vinyl chloride, vinylidine chloride, vinyl acetate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isoprene, isobutylene, chloroprene, hydroxypropyl acrylate, hydroxyethyl acrylate, hydropropyl methacrylate, hydroxyethyl methacrylate, acrylamide, maleic acid, fumaric acid, itaconic acid, citaconic acid, mesaconic acid, and combinations thereof
  • Suitable bases which can be employed to neutralize the amide modified epoxy resins of the present invention include, for example, amines, alkali metal and alkaline earth metal hydroxides. Particularly suitable bases include, sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide, magnesium hydroxide, ammonia, butylamine, dibutylamine, triethylamine, tributylamine, dimethylethanolamine, methyldiethanolamine, N-methylmorpholine, and combinations thereof.
  • Suitable curing agents which can be employed in the coating compositions with the amide modified epoxy resins include, for example, melamine-aldehyde resins, alkylated melamine-aldehyde resins, urea-aldehyde resins, alkylated urea-aldehyde resins, phenol-aldehyde resins, alkylated phenol-aldehyde resins, blocked isocyanates, and combinations thereof.
  • Particularly suitable curing agents include, for example, hexamethoxymethyl-melamine, commercially available as CYMELTM 303 from American Cyanamide Co., BEETLETM 65, a methylated urea-formaldehyde resin commercially available from American Cyanamide Co., VARCUMTM 1131, a phenolic-type resin, commercially available from Reichhold Chemicals, Inc., and combinations thereof.
  • catalyst promoters or accelerators can be employed. Suitable such promoters or accelerators include, for example, mineral and organic acids, combinations thereof and the like. Particularly suitable such accelerators or promoters include, for example, phosphoric acid, polyphosphoric acid, organic sulfonic acids such as, for example, benzene sulfonic acid, toluene sulfonic acid, and combinations thereof.
  • Suitable solvents which can be employed to prepare solvent borne coatings from the compositions of the present invention include those solvents mentioned above as a reaction medium.
  • additives such as, for example, pigments, dyes, flow control agents, fillers and the like can be added to the coating compositions if desired.
  • the temperature was then cooled to 75°C and 0.81 pbw (0.0083 mole) of maleic anhydride was added. The temperature was maintained at 75°C for 30 minutes. The temperature was adjusted to 100°C and a mixture containing 19.39 pbw (0.19 mole) of styrene, 17.07 pbw (0.20 mole) of methacrylic acid and 0.36 pbw of azobis­isobutyronitrile was slowly added over a period of 1 hour. After adding a mixture of 0.08 pbw of azobisisobutyronitrile and 11.6 pbw of n-butanol, the polymerization was continued at 100°C for 30 minutes.
  • the temperature was adjusted to 75°C and a mixture of 14.58 pbw (0.16 mole) of diethanol amine and 375 pbw of deionized water was added over a period of 1 hour to neutralize the acid groups contained in the reaction product.
  • the reaction was conducted at 75°C for 30 minutes.
  • the resultant product had a non-volatiles content of 21.2% by weight and a Brookfield viscosity of 2800 cps (2.8 Pa ⁇ s) at 25°C and pH of 8.6.
  • a coating was prepared by blending 38 pbw of the amide modified epoxy resin prepared in example 1 at 21% by weight non-volatiles, 0.9 pbw of hexamethoxymethyl melamine (commercially available from American Cyanamid as CymelTM 303) and 0.44 pbw of p-­toluene sulfonic acid as a catalyst promoter.
  • This coating was applied to unpolished cold rolled steel panels via a No. 6 Meyer wound wire rod to provide a coating thickness of 0.4 mil (0.01 mm).
  • the coated panels were baked in an oven at 310°F (154°C) for 10 minutes. The following tests were performed on the resultant coated panels.
  • the coated panel was impacted with a falling weight from a calibrated height to give an impact up to 180 in.-lb (20.34 J).
  • An HCl-CuSO4-water solution was applied to the impact spot for 5 minutes to check for failure.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paints Or Removers (AREA)
  • Epoxy Resins (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
EP87115970A 1986-11-07 1987-10-30 Durch Amid modifizierte Epoxydharze Ceased EP0266694A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US06/928,485 US4721742A (en) 1986-11-07 1986-11-07 Amide modified epoxy resins from a dialkanolamine, a monoalkanolamine, an anhydride and (an) unsaturated monomer(s)
US928485 1986-11-07

Publications (2)

Publication Number Publication Date
EP0266694A2 true EP0266694A2 (de) 1988-05-11
EP0266694A3 EP0266694A3 (de) 1989-08-16

Family

ID=25456300

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87115970A Ceased EP0266694A3 (de) 1986-11-07 1987-10-30 Durch Amid modifizierte Epoxydharze

Country Status (8)

Country Link
US (1) US4721742A (de)
EP (1) EP0266694A3 (de)
JP (1) JPH02502193A (de)
KR (1) KR920002772B1 (de)
AU (1) AU596259B2 (de)
BR (1) BR8707881A (de)
NO (1) NO883020D0 (de)
WO (1) WO1988003544A1 (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT388739B (de) * 1987-05-18 1989-08-25 Vianova Kunstharz Ag Verfahren zur herstellung von selbstvernetzenden kationischen lackbindemitteln auf basis von ureidmodifizierten epoxidharzen und deren verwendung
JPS6429466A (en) * 1987-07-25 1989-01-31 Kansai Paint Co Ltd Coating resin composition
US4946911A (en) * 1989-05-22 1990-08-07 The Dow Chemical Company Epoxy resin and water borne coatings therefrom
JPH04268319A (ja) * 1991-02-22 1992-09-24 Dow Chem Nippon Kk 水分散可能なエポキシ樹脂及びその製造方法

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2848433A (en) * 1953-12-30 1958-08-19 Aries Lab Inc Copolymerized and cross-linked epoxide resins
FR1141859A (fr) * 1963-01-28 1957-09-11 Support en tôle assemblée plus spécialement pour les constructions des couvertures et procédés de fabrication
US3716402A (en) * 1971-05-24 1973-02-13 Celanese Coatings Co Film forming compositons from polycarboxylic acids and adducts of polyepoxides and amines
US3960795A (en) * 1974-08-13 1976-06-01 Ppg Industries, Inc. Hydrolyzed reaction product of a polyepoxide with a phenolic compound having a group hydrolyzable to carboxyl
US4088708A (en) * 1975-06-13 1978-05-09 The B. F. Goodrich Company Thermoplastic, thermosetting elastomeric compositions and methods for making the same
US4212781A (en) * 1977-04-18 1980-07-15 Scm Corporation Modified epoxy resins, processes for making and using same and substrates coated therewith
US4098744A (en) * 1977-03-28 1978-07-04 Shell Oil Company Curable water-borne epoxy resin coating compositions
US4094844A (en) * 1977-03-28 1978-06-13 Shell Oil Company Water-borne epoxy resin coating compositions
US4292195A (en) * 1977-05-16 1981-09-29 The B. F. Goodrich Company Non-fugitive antioxidants
JPS5586850A (en) * 1978-05-18 1980-07-01 Dainippon Toryo Co Ltd Cathodic electro-deposition coating composition
CA1186846A (en) * 1978-06-12 1985-05-07 George L. Brown Aqueous emulsion coatings composition comprising self-emulsifiable epoxy ester copolymer mixture
US4176221A (en) * 1978-07-14 1979-11-27 Celanese Polymer Specialties Company Soluble resinous products of polyepoxide-amine adducts and cyclic dicarboxylic acid anhydrides
US4174333A (en) * 1978-11-02 1979-11-13 Ppg Industries, Inc. Carboxylated amide polymers and coating compositions containing same
US4317757A (en) * 1980-01-25 1982-03-02 Shell Oil Company Water-thinnable epoxy resin-sulphanilic acid binder compositions
US4304889A (en) * 1980-07-11 1981-12-08 Texaco Inc. Solvent resistant epoxy coatings
DE3336749A1 (de) * 1983-10-08 1985-04-18 Herberts Gmbh, 5600 Wuppertal Kathodisch abscheidbares waessriges elektrotauchlack-ueberzugsmittel und dessen verwendung
US4476259A (en) * 1983-12-27 1984-10-09 Ford Motor Company Thermosetting coating composition--VI
DE3422472A1 (de) * 1984-06-16 1985-12-19 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung amidgruppen enthaltender epoxid/amin-addukte
US4619952A (en) * 1984-08-02 1986-10-28 Ppg Industries, Inc. Resinous blends of epoxy and acrylic resins and the use thereof in electrodeposition

Also Published As

Publication number Publication date
JPH02502193A (ja) 1990-07-19
EP0266694A3 (de) 1989-08-16
AU596259B2 (en) 1990-04-26
NO883020L (no) 1988-07-06
BR8707881A (pt) 1989-10-03
KR890700150A (ko) 1989-03-10
WO1988003544A1 (en) 1988-05-19
AU8325187A (en) 1988-06-01
US4721742A (en) 1988-01-26
NO883020D0 (no) 1988-07-06
KR920002772B1 (ko) 1992-04-03

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